CN102459413A - Method of preparing a heat-resistant polyamide - Google Patents
Method of preparing a heat-resistant polyamide Download PDFInfo
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- CN102459413A CN102459413A CN2009801597426A CN200980159742A CN102459413A CN 102459413 A CN102459413 A CN 102459413A CN 2009801597426 A CN2009801597426 A CN 2009801597426A CN 200980159742 A CN200980159742 A CN 200980159742A CN 102459413 A CN102459413 A CN 102459413A
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- chemical formula
- aliphatic hydrocarbon
- aromatic hydrocarbon
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- hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method of preparing a heat-resistant polyamide by carrying out condensation polymerization with a monomer mixture including a diester compound and a diamine compound. The present invention can provides an economical method of preparing the heat-resistant polyamide in that a monomer, a raw material, is simply and chiefly prepared, and the polymerizing reaction time is short because it does not need a solvent separately.
Description
Technical field
The present invention relates to a kind of method for preparing polymeric amide; In particular to a kind of method for preparing the economy of heat resistant poly acid amides; This is that a kind of monomer (a kind of raw material) simply and is mainly prepared, and polymerization reaction time is short, because it need not to use separately solvent.
Background technology
Be widely used in fiber, film, thin slice, injection molded article etc. by the polymeric amide of nylon 6 and nylon 66 expressions owing to its outstanding mechanical property and chemical resistant properties.But a problem is arranged, and nylon 6 and nylon 66 thermotolerance when being applied to semiconductor processing equipment, circuit card, automobile and airplane component etc. is not enough, because their melt temperature is respectively 230 ℃ and 260 ℃, so does not possess enough thermotolerances.
For solving about stable on heating problem, through the nylon 46 that made tetramethylenediamine and hexanodioic acid prepared in reaction, it has 290 ℃ higher relatively melt temperature.But; Thereby it has high amido linkage density and has water absorbability; Limit it and used, and used aromatic dicarboxylic acid and aromatic diamines to replace aliphatic dicarboxylic acid or aliphatie diamine and the monomer of the aromatic polyamide that obtains is expensive, also limited the widely-used of it.
In addition, also has the high heat resistance resin, like polyimide, polyetherketone, aromatic polyamide, polyphenylene sulfide etc.But their shortcoming is their also costliness and preparing method's complicacies.
That is to say; The method that prepare at present polymeric amide is through the salt of preparation dicarboxylicacid and diamines in di-alcohol, salt is therefrom separated, isolating salt is dissolved in the high amounts of solvents (for example a large amount of water), at high temperature under pressure and vacuum condition, carries out except that anhydrating etc., so these methods are complicated.In addition, these methods are all uneconomical, because these methods will consume a large amount of water, and need a lot of energy to anhydrate to remove.
Summary of the invention
For solving above-mentioned prior art problems, one aspect of the invention provides a kind of method for preparing the heat resistant poly acid amides, is that a kind of monomer (a kind of raw material) simply and is mainly prepared.
For reaching this technical elements; The invention provides a kind of preparation and contain method by the heat resistant poly acid amides of the repeating unit of chemical formula 3 expression, through a kind of monomer mixture polycondensation of the diamine compound that comprises the diester compound represented by Chemical formula 1 and represented by Chemical formula 2 is carried out:
Chemical formula 1
R wherein
1Be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon.
Chemical formula 2
H
2N-R
2-NH
2
R wherein
2Be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon.
Chemical formula 3
R wherein
2Be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon.
Here, the diamine compound of being represented by Chemical formula 2 can be hexamethylene-diamine (HMDA) or 2-methyl isophthalic acid, 5-pentamethylene diamine (MPDA).
In addition, monomer mixture also can comprise a kind of dicarboxylicacid by following chemical formula 4 expressions:
Chemical formula 4
R wherein
3Be C
2-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon.
Embodiment
Hereinafter will be set forth the present invention in more detail.
The heat resistant poly acid amides of one embodiment of the invention can prepare through making the diester compound of being represented by Chemical formula 1 and the diamine compound polymerization of being represented by Chemical formula 2, and wherein said diester compound can reduce a kind of aromatic ring of aromatic diester compound through hydrogenization and obtain.
Because the aromatic diester compound is inexpensive and it is synthetic 1 of the existing polymeric amide that is used to prepare; The midbody of 4-cyclohexane dicarboxylic acid; Therefore an advantage of the present invention is, compared with prior art, can prepare polymeric amide at low cost through reducing reactions step.
In addition, it is that reaction is simple and speed of reaction is fast that the present invention also has an advantage, because the diester compound of being represented by Chemical formula 1 is soluble in the diamine compound of being represented by Chemical formula 2, and it does not need to use separately solvent.Therefore, the present invention does not need separated salt, isolating salt is dissolved under high temperature and vacuum condition, removes the step of anhydrating in a kind of solvent (comprising water) then, therefore an advantage of the invention is to have reduced and removes the huge energy loss of desolvating.It is to reduce the production cost of final product heat resistant poly acid amides greatly that the present invention also has an advantage, because it is simple to carry out the equipment of this method, and can simplify process thus.
In the method for preparing the heat resistant poly acid amides of one embodiment of the invention, the heat resistant poly acid amides can and carry out polycondensation by the diamine compound that Chemical formula 2 is represented through the diester compound that will be represented by Chemical formula 1 and prepare, shown in following reaction formula 1:
Reaction formula 1
Wherein,
R
1And R
2Can be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon, and preferred C
1-C
14Aliphatic hydrocarbon or C
6-C
14Aromatic hydrocarbon.More preferably, the R in the Chemical formula 1
1Can be C
1-C
6Alkyl.Most preferably, the compound of being represented by Chemical formula 1 can be 1,4-cyclohexane dicarboxylic acid dimethyl esters (or dimethyl cyclohexane 1, the 4-dicarboxylic ester), also promptly, the R in the Chemical formula 1
1Be methyl.
In addition, preferably, the R in the Chemical formula 2
2Be C
1-C
10Straight chain or straight-chain alkyl-sub-.More preferably, the diamine compound of being represented by Chemical formula 2 can be hexamethylene-diamine (HMDA) or 2-methyl isophthalic acid, 5-pentamethylene diamine (MPDA).
In addition, the diester compound of being represented by Chemical formula 1 can be prepared by the hydrogen reduction reaction of aromatic diester compound, shown in following reaction formula 2:
Reaction formula 2
Wherein, R
1Can be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon, and preferred C
1-C
14Aliphatic hydrocarbon or C
6-C
14Aromatic hydrocarbon.
The aromatic diester compound can be dimethyl terephthalate ester or terephthalic acid diaryl ester.When the aromatic diester compound is dimethyl terephthalate ester, R
1Most preferably can be C
1-C
6Alkyl, as stated.
1,4-cyclohexane dicarboxylic acid (CHA) is used for the method for prior art for preparing heat resistant poly acid amides, and said 1, and the 4-cyclohexane dicarboxylic acid is by a kind of terephthalate, particularly dimethyl terephthalate ester preparation.The used said aromatic diester compound of the present invention is synthetic said 1 in the prior art, the midbody that the 4-cyclohexane dicarboxylic acid is used.Therefore, through reducing the W-response step of preparation polymeric amide, the present invention can prepare the heat resistant poly acid amides more economical and more quickly.
The present invention also provides a kind of multipolymer by chemical formula 5 expression, and it is through will be by the aliphatics of chemical formula 4 expressions or aromatic dicarboxylic acid together with the diester compound of being represented by Chemical formula 1 with carry out polycondensation by the diamine compound that Chemical formula 2 is represented and prepare; With a kind of method for preparing said multipolymer:
Chemical formula 5
Wherein,
R
2Be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon, and preferred C
1-C
14Aliphatic hydrocarbon or C
6-C
14Aromatic hydrocarbon.
R
3Be C
2-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon.
N is a natural number of 1 to 999, and
M is a natural number of 1 to 999.
Most preferably, R
2Can be C
1-C
10The straight or branched alkylidene group, R
3Can be C
2-C
6Alkylidene group or phenylene.
Especially, can be preferably at least a in the diacid of selecting oneself, Succinic Acid, terephthalic acid, m-phthalic acid, phthalic acid and the Tetra hydro Phthalic anhydride by the dicarboxylicacid of chemical formula 4 expression.
Shown in following reaction formula 3; The multipolymer of chemical formula 5 can through with a kind of except the mixture of the diamine compound that comprises the diester compound represented by Chemical formula 1 and represent by Chemical formula 2, also comprise monomer mixture by the aliphatics of chemical formula 4 expressions or aromatic dicarboxylic acid and carry out polycondensation and prepare.As indicated above; When through will join the diester compound of representing by Chemical formula 1 and carry out polycondensation in the diamine compound of representing by Chemical formula 2 the time by the dicarboxylicacid of chemical formula 4 expression, the mol ratio of the dicarboxylicacid that its advantage is wherein to add through suitable control and easily control the melt temperature of heat resistant poly acid amides.
Reaction formula 3
Wherein,
R
1And R
2Can be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon, and preferred C
1-C
14Aliphatic hydrocarbon or C
6-C
14Aromatic hydrocarbon; And
R
3Can be C
2-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon, and preferred C
2-C
6Alkylidene group or phenylene.
The concrete grammar of the polycondensation through above-mentioned prepared in reaction heat resistant poly acid amides is following:
At first, diester compound and one of diamine compound introducing are furnished with in the autoclave reactor of whisking appliance and reflux.When preparing the multipolymer of representing by chemical formula 5, also aliphatics or aromatic dicarboxylic acid are introduced wherein.
After introducing reactant, stir this autoclave reactor its temperature that raises simultaneously.When the inside reactor temperature increases to 65 ℃ or when higher, alcohol is distilled out, adopt condensing surface that it is collected.
Half when collecting pure theoretical content uses a kind of rare gas element, and like the air in the replacement reactor drums such as nitrogen, argon gas, and sealed reactor is to increase the internal pressure of reactor drum.
Reaction is through being elevated to temperature of reaction 300 to 400 ℃, and reaction stirred 1 hour to 3 hours, preferred 1 hour 45 minutes to 2 hours 15 minutes and more preferably from about 2 hours and carry out.At this moment, use the internal pressure of a valve controlling reactor to be no more than 20kgf/cm
2
Slowly open valve; Make the internal pressure of reactor drum become barometric point; Use vacuum pump that the internal pressure of reactor drum further is reduced to 1 holder or lower then, continue then to stir 2 hours to 4 hours, preferred 2 hours 30 minutes to 3 hours 30 minutes and more preferably from about 3 hours.
When---loading on the moment of torsion or the electric current (current) of whisking appliance through measurement---when reactant viscosity reaches desirable value, with rare gas element, like nitrogen, argon gas etc., injecting reactor to be discharging vacuum, and utilizes the injection pressure of rare gas element that product is discharged.
When needing, can carry out extra solid-state polymerization reaction.Said solid-state polymerization can carry out as follows: the polymerization section (polymerized chip) that will have certain size is incorporated in the reactor drum of being furnished with whipping appts; On the second-order transition temperature of elevated temperature to polymerization section, then to wherein nitrogen injection or argon gas or make reactor drum form vacuum.
As implied above; The present invention prepares the method for heat resistant poly acid amides and has used the inexpensive monomers that can easily prepare through hydrogenization, and does not comprise separated salt, uses a large amount of water to take the salt of separated and dissolved as solvent and remove and anhydrate that these are complicated and need the complex process of huge energy.Therefore, the present invention can provide the simple and economic method of preparation heat resistant poly acid amides, because step of polymerization is short, and greatly reduces energy waste.
Hereinafter has provided preferred embodiment and comparative example for understanding the present invention.But following examples are merely elaboration the present invention, and the invention is not restricted to this, also are not limited.
Embodiment 1
1 of 200g (1 equivalent), the hexamethylene-diamine (Aldrich Co.) of 4-cyclohexane dicarboxylic acid dimethyl esters (Aldrich Co., cis and trans mixture) and 233g (2 equivalent) adds in the autoclave reactor, then to its stirring and mixing.After being warming up to 750 ℃, collect the methyl alcohol of evaporation through condenser condenses.When distilling out 32g methyl alcohol, nitrogen is injected into removes oxygen in the reactor drum, valve-off is warming up to 400 ℃ afterwards, then mixture is stirred 2 hours.Slowly open valve, make the internal pressure of reactor drum be reduced to barometric point, make its pressure become 1 holder or lowlyer made polymerization of mixtures 3 hours through making reactor drum form vacuum then.Open valve then, nitrogen injection to be discharging vacuum afterwards, thereby polymeric heat resistant poly acid amides is discharged through one of reactor drum lower tapping equipment, and the polymeric amide of discharge cools off in water, adopts cutting machine to process to have the section of certain size then.
Embodiment 2
This basis of heat resistant poly carboxamido-group prepares with embodiment 1 identical method, and difference is to use the 2-methyl isophthalic acid, and the 5-pentamethylene diamine replaces hexamethylene-diamine.
Embodiment 3
This basis of heat resistant poly carboxamido-group prepares with embodiment 1 identical method; Difference is with 1 of 228g (1 equivalent); 4-cyclohexane dicarboxylic acid diethyl ester (or diethyl cyclohexane-1,4-dicarboxylic ester) replaces 1 of 200g (1 equivalent), 4-cyclohexane dicarboxylic acid dimethyl esters.
At this; Said 1; 4-cyclohexane dicarboxylic acid diethyl ester is synthesized through carrying out transesterification reaction according to following method: with 1 normal 1; 4-cyclohexane dicarboxylic acid dimethyl esters and 2 normal dissolve with ethanol are removed methyl alcohol then when adopting Dean and Stark apparatus (dean-stack device) that it is refluxed in YLENE.
Embodiment 4
This basis of heat resistant poly carboxamido-group prepares with embodiment 1 identical method; Difference is with 1 of 256g (1 equivalent); 4-cyclohexane dicarboxylic acid dipropyl (or dipropyl hexanaphthene-1,4-dicarboxylic ester) replaces 1 of 200g (1 equivalent), 4-cyclohexane dicarboxylic acid dimethyl esters.
At this; Said 1; 4-cyclohexane dicarboxylic acid dipropyl is synthesized through carrying out transesterification reaction according to following method: with 1 normal 1; 4-cyclohexane dicarboxylic acid dimethyl esters and 2 normal propyl alcohol are dissolved in the YLENE, when adopting Dean and Stark apparatus that it is refluxed, remove methyl alcohol then.
Embodiment 5
This basis of heat resistant poly carboxamido-group prepares with embodiment 1 identical method; Difference is with 1 of 284g (1 equivalent); 4-cyclohexane dicarboxylic acid dibutyl ester (or dibutyl hexanaphthene-1,4-dicarboxylic ester) replaces 1 of 200g (1 equivalent), 4-cyclohexane dicarboxylic acid dimethyl esters.
At this; Said 1; 4-cyclohexane dicarboxylic acid dibutyl ester synthesizes through carrying out transesterification reaction according to following method: with 1 normal 1; 4-cyclohexane dicarboxylic acid dimethyl esters and 2 normal butanols are dissolved in the YLENE, when adopting Dean and Stark apparatus that it is refluxed, remove methyl alcohol then.
Embodiment 6
This basis of heat resistant poly carboxamido-group prepares with embodiment 1 identical method; Difference is with 1 of 324g (1 equivalent); 4-cyclohexane dicarboxylic acid diphenyl (or phenylbenzene hexanaphthene-1,4-dicarboxylic ester) replaces 1 of 200g (1 equivalent), 4-cyclohexane dicarboxylic acid dimethyl esters.
At this; Said 1; 4-cyclohexane dicarboxylic acid diphenyl is synthesized through carrying out transesterification reaction according to following method: with 1 normal 1; 4-cyclohexane dicarboxylic acid dimethyl esters and 2 normal phenol are dissolved in the YLENE, when adopting Dean and Stark apparatus that it is refluxed, remove methyl alcohol then.
The details of embodiment 1 to 6 is listed in the table below in 1.
Table 1
The comparative example 1 to 6
This basis of heat resistant poly carboxamido-group prepares with embodiment 1 identical method; Difference is to replace 1 normal 1 with listed dicarboxylicacid in the 1 normal following table 2; 4-cyclohexane dicarboxylic acid dimethyl esters, and replace 2 normal hexamethylene-diamines with listed diamines in the 2 normal following tables 2.
Table 2
Embodiment 7 to 36
This basis of heat resistant poly carboxamido-group prepares with embodiment 1 identical method; Difference is to use 1 normal 1; The dicarboxylicacid of listed following mol ratio replaces 1 normal 1 in 4-cyclohexane dicarboxylic acid dimethyl esters (CHDR) and the following table 3; 4-cyclohexane dicarboxylic acid dimethyl esters, and use hexamethylene-diamine (HMDA) listed in the 2 normal following tables 3 or 2 normal 2-methyl isophthalic acids, 5-pentamethylene diamine (MPDA) replaces 2 normal hexamethylene-diamines.
Table 3
-: the embodiment that thermal destruction takes place before fusing point
EXPERIMENTAL EXAMPLE
The character of the heat resistant poly acid amides for preparing among embodiment and the comparative example is measured through following method, and the result lists in above-mentioned table 1 in 3.
Viscosity
The viscosity of the heat resistant poly acid amides through method for preparing is measured at 35 ℃ of following employing ostwald's viscometers (Ostwald Viscosimeter) after said polymeric amide being dissolved in the meta-cresol.
Fusing point
Fusing point adopts a DSC (DSC) to measure with 10 ℃/minute sweep velocity.
As shown in table 1; Polymeric amide according to the preparation of the method for embodiment 1 to 6 demonstrates the fusing point that is suitable for the heat resistant poly acid amides; But can find out; Adopt the polymkeric substance of disclosed material simple method preparation among the comparative example 1 to 6 to have good thermotolerance, but their polymerization degree is not high according to the present invention.More specifically, the polymkeric substance among the comparative example is unfavorable, because it needs overwork, as increasing the reaction times or carrying out solid-state polymerization, obtains having the polymkeric substance of high-polymerization degree.But, can find out, can obtain through simple method according to embodiments of the invention polymeric polymkeric substance, and its thermotolerance is still good, and the polymerization degree is also enough.
In addition, can find out from embodiment 7 to 36 that the dicarboxylicacid through also introducing the control mol ratio also carries out polycondensation, the method that the present invention prepares polymeric amide can easily be controlled the melt temperature of the heat resistant poly acid amides of final preparation.
Claims (7)
1. one kind prepares the method that contains by the heat resistant poly acid amides of the repeating unit of chemical formula 3 expression, through a kind of monomer mixture polycondensation of the diamine compound that comprises the diester compound represented by Chemical formula 1 and represented by Chemical formula 2 is carried out:
Chemical formula 1
R wherein
1Be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon,
Chemical formula 2
H
2N-R
2-NH
2
R wherein
2Be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon, and
Chemical formula 3
R wherein
2Be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon.
2. the process of claim 1 wherein R in the Chemical formula 1
1Be C
1-C
6Alkyl, the R in the Chemical formula 2
2Be C
1-C
10The straight or branched alkylidene group.
3. the process of claim 1 wherein that said diamine compound is hexamethylene-diamine (HMDA) or 2-methyl isophthalic acid, 5-pentamethylene diamine (MPDA).
4. the process of claim 1 wherein that said monomer mixture also comprises a kind of dicarboxylicacid by chemical formula 4 expressions:
Chemical formula 4
R wherein
3Be C
2-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon.
5. the method for claim 4, wherein said dicarboxylicacid is the compound of at least a diacid of selecting oneself, Succinic Acid, terephthalic acid, m-phthalic acid, phthalic acid and Tetra hydro Phthalic anhydride.
6. heat resistant poly acid amides that contains by the repeating unit of chemical formula 3 expression, it is by method preparation of one of claim 1 to 5:
Chemical formula 3
R wherein
2Be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon.
7. the heat resistant poly acid amides of claim 6, contain the repeating unit by chemical formula 5 expressions:
Chemical formula 5
Wherein,
R
2Be C
1-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon, and be preferably C
1-C
14Aliphatic hydrocarbon or C
6-C
14Aromatic hydrocarbon;
R
3Be C
2-C
20Aliphatic hydrocarbon or C
6-C
20Aromatic hydrocarbon;
N is a natural number of 1 to 999, and
M is a natural number of 1 to 999.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2009/001857 WO2010117098A2 (en) | 2009-04-10 | 2009-04-10 | Method of preparing a heat-resistant polyamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102459413A true CN102459413A (en) | 2012-05-16 |
Family
ID=42936657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801597426A Pending CN102459413A (en) | 2009-04-10 | 2009-04-10 | Method of preparing a heat-resistant polyamide |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US8822629B2 (en) |
| EP (1) | EP2417185B1 (en) |
| JP (1) | JP5416829B2 (en) |
| CN (1) | CN102459413A (en) |
| ES (1) | ES2628778T3 (en) |
| WO (1) | WO2010117098A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315457A (en) * | 2015-11-06 | 2016-02-10 | 东华大学 | High-molecular-weight heat-temperature-resistant polyamide resin and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2628778T3 (en) | 2009-04-10 | 2017-08-03 | Sk Chemicals, Co., Ltd. | Preparation procedure of a heat resistant polyamide |
| US20130085257A1 (en) * | 2010-06-23 | 2013-04-04 | Asahi Kasei Chemicals Corporation | Methods for producing aqueous diamine dicarboxylic acid salt solution and polyamide |
| CN103403063B (en) * | 2011-03-15 | 2016-01-20 | 旭化成化学株式会社 | Polymeric amide and daiamid composition |
| GB2533284B (en) | 2014-12-11 | 2017-04-12 | Imagination Tech Ltd | Performing object detection |
| ES2945113T3 (en) | 2018-04-26 | 2023-06-28 | Elantas Beck India Ltd | Cardanol-based curing agent for epoxy resin compositions |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3459714A (en) * | 1964-08-05 | 1969-08-05 | Chemische Werke Witten Gmbh | Process for the preparation of polyamides in finely grained form |
| US3516972A (en) * | 1966-04-01 | 1970-06-23 | Chemische Werke Witten Gmbh | Process for the preparation of polyamides in finely divided form |
| US4567249A (en) * | 1983-11-18 | 1986-01-28 | General Electric Company | Melt preparation of polyamide by amide ester interchange |
| CN1049167A (en) * | 1989-07-12 | 1991-02-13 | 阿托化学公司 | Thermotropic semi-aliphatic copolyesteramide and preparation method thereof |
| US5019641A (en) * | 1990-06-06 | 1991-05-28 | General Electric Company | Polyamide from 1,3 propylene diamine and isophthalic acid compound |
| CN1168898A (en) * | 1996-04-04 | 1997-12-31 | M和S研究开发株式会社 | Methnod of producing polyamide resin |
| CN1696201A (en) * | 2004-05-10 | 2005-11-16 | 埃姆斯-切米股份公司 | Thermoplastic polyamide moulded compositions |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3242141A (en) | 1962-12-04 | 1966-03-22 | Gen Mills Inc | Polyamide compositions from fatty dimer diamines |
| DE1770766A1 (en) * | 1968-07-02 | 1971-11-18 | Veba Chemie Ag | Process for the production of transparent polyamides |
| US3629053A (en) * | 1968-10-23 | 1971-12-21 | Kanegafuchi Spinning Co Ltd | Novel polyamide and fiber thereof |
| US3842046A (en) * | 1969-06-26 | 1974-10-15 | Veba Chemie Ag | Polyamides of trimethylhexamethylenediamine cycloaliphatic dicarboxylic acid and carbocyclic aromatic dicarboxylic acid |
| FR2356683A1 (en) * | 1976-06-28 | 1978-01-27 | Rhone Poulenc Ind | NEW COPOLYAMIDES BASED ON HEXAMETHYLENE ADIPAMIDE |
| US4983718A (en) * | 1989-06-09 | 1991-01-08 | General Electric Company | Color minimization during melt preparation of polyamides with hypophosphorus acid |
| AU2002221074A1 (en) * | 2000-12-11 | 2002-06-24 | Asahi Kasei Kabushiki Kaisha | Polyamide |
| JP5149220B2 (en) * | 2009-02-25 | 2013-02-20 | 旭化成ケミカルズ株式会社 | Highly heat-stabilized copolyamide |
| ES2628778T3 (en) | 2009-04-10 | 2017-08-03 | Sk Chemicals, Co., Ltd. | Preparation procedure of a heat resistant polyamide |
-
2009
- 2009-04-10 ES ES09843085.3T patent/ES2628778T3/en active Active
- 2009-04-10 JP JP2012504559A patent/JP5416829B2/en not_active Expired - Fee Related
- 2009-04-10 CN CN2009801597426A patent/CN102459413A/en active Pending
- 2009-04-10 US US13/263,620 patent/US8822629B2/en active Active
- 2009-04-10 EP EP09843085.3A patent/EP2417185B1/en not_active Not-in-force
- 2009-04-10 WO PCT/KR2009/001857 patent/WO2010117098A2/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3459714A (en) * | 1964-08-05 | 1969-08-05 | Chemische Werke Witten Gmbh | Process for the preparation of polyamides in finely grained form |
| US3516972A (en) * | 1966-04-01 | 1970-06-23 | Chemische Werke Witten Gmbh | Process for the preparation of polyamides in finely divided form |
| US4567249A (en) * | 1983-11-18 | 1986-01-28 | General Electric Company | Melt preparation of polyamide by amide ester interchange |
| CN1049167A (en) * | 1989-07-12 | 1991-02-13 | 阿托化学公司 | Thermotropic semi-aliphatic copolyesteramide and preparation method thereof |
| US5019641A (en) * | 1990-06-06 | 1991-05-28 | General Electric Company | Polyamide from 1,3 propylene diamine and isophthalic acid compound |
| CN1168898A (en) * | 1996-04-04 | 1997-12-31 | M和S研究开发株式会社 | Methnod of producing polyamide resin |
| CN1696201A (en) * | 2004-05-10 | 2005-11-16 | 埃姆斯-切米股份公司 | Thermoplastic polyamide moulded compositions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315457A (en) * | 2015-11-06 | 2016-02-10 | 东华大学 | High-molecular-weight heat-temperature-resistant polyamide resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2628778T3 (en) | 2017-08-03 |
| EP2417185A4 (en) | 2013-05-01 |
| WO2010117098A2 (en) | 2010-10-14 |
| US8822629B2 (en) | 2014-09-02 |
| EP2417185B1 (en) | 2017-03-22 |
| JP5416829B2 (en) | 2014-02-12 |
| EP2417185A2 (en) | 2012-02-15 |
| WO2010117098A3 (en) | 2010-12-02 |
| US20120029163A1 (en) | 2012-02-02 |
| JP2012523472A (en) | 2012-10-04 |
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Application publication date: 20120516 |